CN101185891A - Porous carbon supported platinum-cerium oxide catalyst for fuel cell and preparation thereof - Google Patents
Porous carbon supported platinum-cerium oxide catalyst for fuel cell and preparation thereof Download PDFInfo
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- CN101185891A CN101185891A CNA2007101954337A CN200710195433A CN101185891A CN 101185891 A CN101185891 A CN 101185891A CN A2007101954337 A CNA2007101954337 A CN A2007101954337A CN 200710195433 A CN200710195433 A CN 200710195433A CN 101185891 A CN101185891 A CN 101185891A
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- porous carbon
- cerium oxide
- platinum
- catalyst
- fuel cell
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a porous carbon load platinum-cerium oxide catalyst for fuel cells and a preparation method. A carrier of the invention is porous carbon, and a catalyst active component is platinum-cerium oxide, wherein, the cerium-oxide amounts to 5-15% of the weight of the porous carbon cerium oxide; the platinum load is 20-30%. The porous carbon load platinum-cerium oxide composite catalyst exhibits more excellent antitoxic performance than general Vulcan XC-72 carbon load platinum catalyst, and can be applied to proton exchange membrane fuel cells which need to enhance antitoxic performance and direct methanol fuel cells.
Description
Technical field
The present invention relates to a kind of used in proton exchange membrane fuel cell porous carbon supported platinum-cerium oxide composite catalyst and preparation method thereof.
Background technology
Mostly adopt carbon dust as carrier in the existing Proton Exchange Membrane Fuel Cells technology, platinum particles is loaded into the carbon dust surface, obtain loaded carbon supported platinum catalyst.Carbon carrier has big specific area, and mesopore is abundant, is good carrier, can reduce the use amount of noble metal platinum greatly, reduces the battery overall cost.But the problem that this catalyst is poisoned easily also is to hinder the important difficult problem that fuel cell further develops.Hydrogen-oxygen (or hydrogen sky) proton exchange membrane fuel gas can not be hundred-percent pure clean gas, and the inside also has impurity such as CO, H
2S, NH
3Deng, impurity can cause catalyst activity composition-platinosis, thereby loses activity; Have the intermediate product that contains carbonyl to generate in methanol fuel cell especially, the generation of this intermediate is adsorbed on the catalyst activity component platinum, makes it the catalytic action that can not recur, and causes catalyst poisoning.And, since catalyst at low temperatures activity reduce, when causing the fuel cell cold operation, activity of such catalysts is limited.
And the anti-method that adopted of poisoning of present catalyst mostly is adds auxiliary agent in catalyst, noxious material is combined with auxiliary agent stop Toxic to combine with the catalyst activity component.And the metal oxide that adopts the multivalence attitude is the mithridatism that additive increases catalyst, improves the utilization ratio of catalyst, and the price that reduces fuel cell has very important research and practical application meaning.
Summary of the invention
One of purpose of the present invention provides a kind of porous carbon supported platinum-cerium oxide composite catalyst.
Foregoing invention purpose of the present invention reaches by the following technical programs:
A kind of porous carbon supported platinum-cerium oxide catalyst for fuel cell, its carrier are porous carbon, and the catalyst activity component is a platinum-cerium oxide, and wherein, described cerium oxide accounts for the 5-15% of porous carbon cerium oxide weight; The platinum carrying capacity is 20-30%.
A kind of optimal technical scheme is characterized in that: described fuel cell is Proton Exchange Membrane Fuel Cells or DMFC.
Another object of the present invention is to provide the preparation of described porous carbon supported platinum-cerium oxide composite catalyst,
Above-mentioned purpose of the present invention reaches by the following technical programs:
A kind of preparation method of porous carbon supported platinum-cerium oxide catalyst for fuel cell, its step is as follows:
(1) with the porous carbon dust respectively at acetone, dense HNO
3Add hot reflux 1-2 hour in the solution, filter, spend deionised water to pH=6,100-120 ℃ of freeze-day with constant temperature;
(2) take by weighing the porous carbon dust that step (1) handled and place beaker, add isopropyl alcohol and water, add ceric ammonium nitrate solution again, fully mix in the ultrasonic wave, in system, add excessive sodium hydroxide solution, make the pH value, flooded 4-6 hour at 8-9, reaction is carried out suction filtration, washing after finishing, 70-90 ℃ vacuum drying 10-14 hour;
(3) product in the step (2) is placed tube furnace, under N2 atmosphere, calcine, calcined 2-4 hour for 200-400 ℃, get the porous carbon cerium oxide powder material;
(4) step (3) gained porous carbon cerium oxide is put into there-necked flask, add absolute ethyl alcohol, water and isopropyl alcohol successively, ultrasonic mixing adds 10-25mmol/L H
2PtCl
6The solution ultrasonic wave stirs 20-40min, uses 1mol/L Na
2CO
3Solution is regulated pH=8-9, gets the H of carbon containing cerium oxide
2PtCl
6Mixed slurry;
(5) slowly drip excess formaldehyde solution in step (4) gained mixed slurry, temperature is controlled at 55-65 ℃, and logical nitrogen is as protection gas in the course of reaction; ultrasonic wave stirs, and reaction is cooled to room temperature after finishing, and stops ventilation then; carry out vacuum filtration, spend deionised water to there not being Cl
-, filter cake 70-90 ℃ of vacuum drying, is obtained the porous carbon supported platinum-cerium oxide composite catalyst.
Beneficial effect:
Porous carbon supported platinum-cerium oxide composite catalyst material list of the present invention reveals the antitoxin voltinism energy more more remarkable than conventional VulcanXC-72 carbon supported platinum catalyst, therefore be expected to substitute existing conventional carbon supported platinum catalyst, be used for Proton Exchange Membrane Fuel Cells and DMFC that needs improve mithridatism, as also having poisonous impurity at the battery fuel raw material or in reaction, producing under the situation of poisonous intermediate product, the porous carbon supported platinum-cerium oxide catalyst that anti-poisoning ability is strong can more effectively keep the performance of battery, guarantees the stable operation of battery.
Another advantage of the present invention is that preparation process is simple, need not complex device, and the oxidation of coal cerium particle that makes is tiny, is evenly distributed, and has shown remarkable antioxygenic property.
The present invention will be further described below by the drawings and specific embodiments, but and do not mean that limiting the scope of the invention.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the porous carbon ceria oxide powder of one of embodiment of the invention preparation.
Fig. 2 is the XRD figure spectrum of the porous carbon ceria oxide powder of one of embodiment of the invention preparation.
Fig. 3 is the performance variation that porous carbon ceria oxide powder of the present invention is used for Proton Exchange Membrane Fuel Cells.
The specific embodiment
Take by weighing 0.9g porous carbon dust respectively at acetone, dense HNO
3In the solution, added hot reflux 1 hour.Filter, spend deionised water to pH=6,110 ℃ of freeze-day with constant temperature; The porous carbon dust of handling places beaker; add isopropyl alcohol and water; add again ceric ammonium nitrate solution (addition by obtain at last cerium oxide account for porous carbon cerium oxide weight 10%); fully mix in the ultrasonic wave; in system, add excessive sodium hydroxide solution; make the pH value at 8-9; flooded 4-6 hour; after finishing, reaction carries out suction filtration, washing; 80 ℃ of vacuum drying 12 hours place tube furnace with product then, calcine under the N2 protection; calcined 3 hours for 300 ℃, get the porous carbon cerium oxide powder material.
Gained oxidation of coal cerium material is put into there-necked flask, adds absolute ethyl alcohol, water and isopropyl alcohol successively, and ultrasonic mixing adds 19.3mmol/L H
2PtCl
6The solution ultrasonic wave stirs 30min, uses 1mol/LNa
2CO
3Solution is regulated pH=8-9, gets the H of carbon containing cerium oxide
2PtCl
6Mixed slurry slowly drips excess formaldehyde solution again in the gained slurry, temperature is controlled at about 60 ℃; logical nitrogen is as protection gas in the course of reaction, and ultrasonic wave stirs, and is cooled to room temperature after reaction is finished; stop ventilation then, carry out vacuum filtration, spend deionised water to there not being Cl
-, filter cake 80 ℃ of vacuum drying, is obtained porous carbon supported cerium oxide-platinum compound catalyze agent material.The catalyst platinum carrying capacity for preparing is 20%.
The TEM test is carried out on Japanese HITACHI H-700 type transmission electron microscope instrument, and sample, is observed hanging drop on the net in standard copper in ethanol then through ultrasonic dispersion 20min, and multiplication factor is 100000.
As can be seen from Figure 1 even particle distribution does not have obvious agglomeration.
The XRD test is carried out on the XD-D1 type X-ray diffractometer of day island proper Tianjin Shimadzu company, and Cu target, beam wavelength are 0.154056nm.The porous carbon ceria oxide powder that obtains is tested, obtained the XRD figure spectrum of porous carbon ceria oxide powder as shown in Figure 2.
Among Fig. 2, be that 28 °, 33 °, 47 °, 56 °, 69 ° and 76 ° locate then corresponding respectively are CeO at 2 θ
2(111), CeO
2(200), CeO
2(220), CeO
2(311), CeO
2(400) and CeO
2The crystal structure characteristic peak of cubic structure (331) does not find that other contain the characteristic peak of Ce elements material, illustrates that cerium is all with CeO
2Form exist.
Take by weighing 0.8g porous carbon dust respectively at acetone, dense HNO
3In the solution, added hot reflux 1 hour.Filter, spend deionised water to pH=6,100 ℃ of freeze-day with constant temperature; The porous carbon dust of handling places beaker, add isopropyl alcohol and water, add again ceric ammonium nitrate solution (addition by obtain at last cerium oxide account for porous carbon cerium oxide weight 20%), fully mix in the ultrasonic wave, in system, add excessive sodium hydroxide solution, make the pH value at 8-9, flooded 4-6 hour, reaction is carried out suction filtration, washing after finishing, 90 ℃ of vacuum drying 11 hours, then product is placed tube furnace, at N
2Calcine under the protection, calcined 2 hours for 400 ℃, get the porous carbon cerium oxide powder material.
It is identical with embodiment 1 to carry the platinum method, and the catalyst platinum carrying capacity for preparing is 30%.
Embodiment 3
Take by weighing 0.9g porous carbon dust respectively at acetone, dense HNO
3In the solution, added hot reflux 2 hours.Filter, spend deionised water to pH=6,120 ℃ of freeze-day with constant temperature; The Vulcan XC-72 carbon dust of handling places beaker, add isopropyl alcohol and water, add again ceric ammonium nitrate solution (addition by obtain at last cerium oxide account for oxidation of coal cerium weight 10%), fully mix in the ultrasonic wave, in system, add excessive sodium hydroxide solution, make the pH value at 8-9, flooded 4-6 hour, reaction is carried out suction filtration, washing after finishing, 70 ℃ of vacuum drying 14 hours, then product is placed tube furnace, at N
2Calcine under the protection, calcined 4 hours for 200 ℃, get the porous carbon cerium oxide powder material.
It is identical with embodiment 1 to carry the platinum method, and the catalyst platinum carrying capacity for preparing is 30%.
Claims (3)
1. porous carbon supported platinum-cerium oxide catalyst for fuel cell, its carrier is a porous carbon, and the catalyst activity component is a platinum-cerium oxide, and wherein, described cerium oxide accounts for the 5-15% of porous carbon cerium oxide weight; The platinum carrying capacity is 20-30%.
2. porous carbon supported platinum-cerium oxide catalyst for fuel cell according to claim 1 is characterized in that: described fuel cell is Proton Exchange Membrane Fuel Cells or DMFC.
3. the preparation method of a porous carbon supported platinum-cerium oxide catalyst for fuel cell, its step is as follows:
(1) with the porous carbon dust respectively at acetone, dense HNO
3Add hot reflux 1-2 hour in the solution, filter, spend deionised water to pH=6,100-120 ℃ of freeze-day with constant temperature;
(2) take by weighing the porous carbon dust that step (1) handled and place beaker, add isopropyl alcohol and water, add ceric ammonium nitrate solution again, fully mix in the ultrasonic wave, in system, add excessive sodium hydroxide solution, make the pH value, flooded 4-6 hour at 8-9, reaction is carried out suction filtration, washing after finishing, 70-90 ℃ vacuum drying 10-14 hour;
(3) product in the step (2) is placed tube furnace, at N
2Calcine under the atmosphere, calcined 2-4 hour for 200-400 ℃, get the porous carbon cerium oxide powder material;
(4) step (3) gained porous carbon cerium oxide is put into there-necked flask, add absolute ethyl alcohol, water and isopropyl alcohol successively, ultrasonic mixing adds 10-25mmol/L H
2PtCl
6The solution ultrasonic wave stirs 20-40min, uses 1mol/L Na
2CO
3Solution is regulated pH=8-9, gets the H of carbon containing cerium oxide
2PtCl
6Mixed slurry;
(5) slowly drip excess formaldehyde solution in step (4) gained mixed slurry, temperature is controlled at 55-65 ℃, and logical nitrogen is as protection gas in the course of reaction; ultrasonic wave stirs, and reaction is cooled to room temperature after finishing, and stops ventilation then; carry out vacuum filtration, spend deionised water to there not being Cl
-, filter cake 70-90 ℃ of vacuum drying, is obtained porous carbon supported cerium oxide-platinum composite catalyst.
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| CNB2007101954337A CN100571864C (en) | 2007-11-29 | 2007-11-29 | Porous carbon supported platinum-cerium oxide catalyst for fuel cell and preparation thereof |
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| CN100571864C CN100571864C (en) | 2009-12-23 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101697373B (en) * | 2009-10-23 | 2011-10-12 | 南京大学 | Method for preparing metal oxide-carbon composite materials |
| CN103007934A (en) * | 2012-12-12 | 2013-04-03 | 黑龙江大学 | Preparation method of anode catalyst Pt/CexSn1-xO2 for methanol fuel cell |
| CN103028401A (en) * | 2012-12-13 | 2013-04-10 | 北京化工大学常州先进材料研究院 | Direct methanol fuel cell anode catalyst and preparation method thereof |
| CN103949246A (en) * | 2014-05-19 | 2014-07-30 | 哈尔滨工业大学 | Method for preparing platinum catalyst using porous foamed titanium as carrier for methanol reforming combustion chamber |
| CN103949245A (en) * | 2014-05-19 | 2014-07-30 | 哈尔滨工业大学 | Preparation method of micro methyl alcohol reformer combustion chamber catalyst |
| CN109621951A (en) * | 2018-12-31 | 2019-04-16 | 内蒙古大学 | A kind of three-way catalyst and preparation method thereof preparing glyceric acid for aoxidizing glycerol |
| CN117543035A (en) * | 2024-01-10 | 2024-02-09 | 华北电力大学 | Nafion-C/CeO 2 Pt composite membrane and preparation method and application thereof |
| CN117543035B (en) * | 2024-01-10 | 2024-04-26 | 华北电力大学 | Nafion-C/CeO2Pt composite membrane and preparation method and application thereof |
-
2007
- 2007-11-29 CN CNB2007101954337A patent/CN100571864C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101697373B (en) * | 2009-10-23 | 2011-10-12 | 南京大学 | Method for preparing metal oxide-carbon composite materials |
| CN103007934A (en) * | 2012-12-12 | 2013-04-03 | 黑龙江大学 | Preparation method of anode catalyst Pt/CexSn1-xO2 for methanol fuel cell |
| CN103007934B (en) * | 2012-12-12 | 2014-05-07 | 黑龙江大学 | Preparation method of anode catalyst Pt/CexSn1-xO2 for methanol fuel cell |
| CN103028401A (en) * | 2012-12-13 | 2013-04-10 | 北京化工大学常州先进材料研究院 | Direct methanol fuel cell anode catalyst and preparation method thereof |
| CN103949246A (en) * | 2014-05-19 | 2014-07-30 | 哈尔滨工业大学 | Method for preparing platinum catalyst using porous foamed titanium as carrier for methanol reforming combustion chamber |
| CN103949245A (en) * | 2014-05-19 | 2014-07-30 | 哈尔滨工业大学 | Preparation method of micro methyl alcohol reformer combustion chamber catalyst |
| CN103949245B (en) * | 2014-05-19 | 2016-03-16 | 哈尔滨工业大学 | The preparation method of miniature methanol reformer combustion chamber catalyst |
| CN103949246B (en) * | 2014-05-19 | 2016-06-08 | 哈尔滨工业大学 | Preparation method for the platinum catalyst that methanol recapitalization combustor is carrier with porous foam titanium |
| CN109621951A (en) * | 2018-12-31 | 2019-04-16 | 内蒙古大学 | A kind of three-way catalyst and preparation method thereof preparing glyceric acid for aoxidizing glycerol |
| CN117543035A (en) * | 2024-01-10 | 2024-02-09 | 华北电力大学 | Nafion-C/CeO 2 Pt composite membrane and preparation method and application thereof |
| CN117543035B (en) * | 2024-01-10 | 2024-04-26 | 华北电力大学 | Nafion-C/CeO2Pt composite membrane and preparation method and application thereof |
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| CN100571864C (en) | 2009-12-23 |
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